JP5072858B2 - Intermediate layer containing stabilized infrared absorber - Google Patents

Description

  The present invention is in the field of polymer sheets and multi-layer sheet glass panels containing infrared absorbers, and more specifically, the invention relates to polymer sheets containing infrared absorbers that selectively absorb infrared radiation. And in the field of multi-layer flat glass panels.

  Poly (vinyl butyral) (PVB) is commonly used in the manufacture of polymer sheets that can be used as interlayers in light transmissive laminates such as safety glass or polymer laminates. Safety glass often refers to a transparent laminate comprising a poly (vinyl butyral) sheet placed between two glass sheets. Safety glass is often used to provide transparent barriers in buildings and automobile openings. Its main function is to damage the objects or human beings in the enclosed area without allowing energy such as that caused by the blowout from the object to enter through the opening or the dispersion of glass fragments. Or to absorb with minimal injury. The safety glass also provides other advantageous effects, such as reduced acoustic noise, reduced UV and / or IR light transmission, and / or the appearance and aesthetics of the window opening. It can also be used to increase the attractiveness.

  In many applications, it is desirable to use safety glass that not only has the appropriate physical performance characteristics for the chosen application, but also has a light transmission that is particularly suitable for the end use of the product. For example, in many cases it is desirable to limit infrared radiation transmission through laminated safety glass to provide improved thermal properties.

  The ability to reduce the transmission of infrared radiation, especially near infrared radiation, is a particularly desirable property of multi-layer glazing panels, especially safety glass used in automotive and building applications. Decreasing the transmittance of infrared radiation leads to a reduction in the heat generated by such radiation in a closed space.

Numerous examples exist in the field of compositions and methods for reducing infrared radiation transmission through multi-layer glazing panels. Among these is the use of agents that selectively absorb radiation in the infrared region. One effective known agent is lanthanum hexaboride (LaB ₆ ). Lanthanum hexaboride is an excellent selective absorber of near-infrared radiation, but undergoes molecular degradation due to commonly encountered environmental conditions found in the intermediate layer that compromise the infrared absorption capability of the intermediate layer.

  Further improved compositions and methods enhance the properties of multi-layer glazing panels containing infrared absorbers, in particular multi-layer glazing panels containing lanthanum hexaboride, and are stable without adversely affecting optical properties. Needed to give sex.

  The present invention includes an intermediate layer and a multi-layer flat glass panel including the intermediate layer, and the intermediate layer includes lanthanum hexaboride and an epoxy agent. The addition of the epoxy agent surprisingly provides a stabilizing effect on lanthanum hexaboride, which advantageously absorbs infrared radiation and allows the production of an intermediate layer that is resistant to environmental degradation.

(Details of the invention)
The present invention includes infrared absorbers and their use in interlayers as well as multi-layer glazing panels comprising this interlayer.

  As used herein, "multi-layer glass sheet interlayer" refers to an interlayer that can be used in sheet glass having more than one layer, for example, two glass sheet glasses having an interlayer therebetween. Means. The intermediate layer can consist of a single polymer layer or multiple layers combined. Sheet glass panels can be used, for example, in automotive windshields and architectural applications. As disclosed herein, lanthanum hexaboride and an epoxy agent are introduced into or on a polymer sheet useful as an interlayer or as a layer in an interlayer for use in multi-layer glazing panel applications. The As explained in detail below, the polymer sheet of the present invention can comprise any suitable polymer, and in a preferred embodiment, the polymer sheet comprises poly (vinyl butyral).

  Prior attempts in the art to reduce infrared radiation have been found on various infrared reflective layers (see, eg, US Pat. Nos. 6,391,400, 5,245,468, and 2002/0150744) or polymer layers. Alternatively, various infrared absorbers dispersed therein (for example, US Pat. Nos. 6,737,159, 6,506,487, 6,620,872, 6,673,456, 2002/0054993, 2003/0094600, 2003/0122114). No., 2003/0054160, and International Patent Application WO 02/077081). However, the use of a separate infrared reflective layer requires time-consuming and inefficient processing steps, while the use of infrared absorbers presents several difficulties, among them environmental conditions such as There is a gradual deterioration of these agents due to high humidity conditions or acidic conditions.

  The present invention includes an intermediate layer comprising lanthanum hexaboride and an epoxy agent. As described in detail below, any suitable lanthanum hexaboride and epoxy agent can be used.

  The lanthanum hexaboride and epoxy agents of the present invention can be disposed on or in one or more layers of the intermediate layer. In various embodiments, the lanthanum hexaboride and the epoxy agent are disposed in or on the polymer sheet introduced in the intermediate layer. In these embodiments, the intermediate layer can comprise only a single polymer sheet, or it can be a multi-layer intermediate layer comprising a polymer sheet. Embodiments in which multiple interlayers are used include those known in the art, for example, an interlayer in which two or more polymer sheets are laminated together to form a single interlayer, and 1 Including, but not limited to, an intermediate layer having one or more polymer sheets laminated together with one or more polymer films. In any of these embodiments, the lanthanum hexaboride and the epoxy agent can be disposed on or in any one or more of the layers comprising the polymer sheet and the polymer film, the various layers being Can be the same or different.

Exemplary multi-layer interlayer structures include:
(Polymer sheet) _n
(Polymer sheet / Polymer film / Polymer sheet) _p
(Where n is 1 to 10, in various embodiments less than 5 and p is 1 to 5 and in various embodiments less than 3).

  The interlayer of the present invention can be introduced into a multi-layer glazing panel, and in various embodiments is introduced between two layers of glass. Applications of such structures include automobile windshields and building glass.

  In embodiments where the interlayer is disposed between two layers of glass, the interlayer of the present invention incorporating the lanthanum hexaboride and epoxy agent of the present invention is exposed to the environment at the edge of the multi-layer glazing panel. It is particularly useful in places such as automobile windshields and side windows.

In other embodiments of the invention, an interlayer comprising an infrared absorber is used in the bilayer. As used herein, a bilayer is a multi-layer structure having a rigid substrate having an intermediate layer disposed thereon, such as glass or acrylic. A common double layer structure is (glass) // (polymer sheet) // (polymer film). The infrared absorbers of the present invention are particularly useful for bilayers because the exposed polymer film generally allows moisture ingress through the polymer film and into the polymer sheet. As a double layer structure, for example,
(Glass) // (Polymer sheet) _h // (Polymer film) _g
(Glass) // (polymer sheet) _h // (polymer film)
(Where h is 1 to 10, in various embodiments less than 3 and g is 1 to 5 and in various embodiments is less than 3), but is not limited thereto. .

In a further embodiment, the intermediate layer can thus be, for example, a spall shield:
(Multi-layer plate glass panel) // (Polymer sheet) _h // (Polymer film) _g
(Multi-layer glass plate panel) // (Polymer sheet) _h // (Polymer film)
(Where h is 1 to 10 and in various embodiments is less than 3 and g is 1 to 5 and in various embodiments is less than 3). Although it can add to one side of a panel, it is not limited to these.

  In addition to the lanthanum hexaboride and epoxy agents of the present invention, one or more conventional infrared absorbers or infrared reflective layers can be introduced into the interlayer of the present invention.

  In various embodiments, solar control glass (solar glass) is used for one or more multi-layer glass panels of the present invention. Solar glass can be any conventional glass that introduces one or more additives to improve the optical properties of the glass, in particular solar glass such as radiation, eg near infrared and ultraviolet Generally formulated to reduce or eliminate transmission of unwanted wavelengths. Solar glass can also be colored, which provides a desirable reduction in visible light transmission for some applications. Examples of solar glasses useful in the present invention include bronze glasses, gray glasses, low E (low emissivity) glasses known in the art, including those described in US Pat. Nos. 6,737,159 and 6,620,872. And solar glass panels. As explained below, hard substrates other than glass can be used.

  In various embodiments of the present invention, the lanthanum hexaboride and epoxy agents of the present invention are distributed on or in a polymer sheet and / or polymer film. The concentration of lanthanum hexaboride and epoxy agent, and the ratio between them, can be adjusted to meet the needs of a particular application. In general, the level of lanthanum hexaboride is sufficient to provide the desired infrared absorption on the sheet, and the epoxy agent is included in an amount sufficient to provide the desired stability, depending on the application. .

  In various embodiments, a polymer sheet of the present invention comprising lanthanum hexaboride and an epoxy agent is at least 5%, at least 15%, at least 25%, at least 25% of infrared radiation from 700 nanometers to 2,000 nanometers. Absorbs 50%, at least 75%, or at least 90%, while transmitting at least 60%, at least 70%, at least 80%, at least 90%, or at least 95% of visible light.

Lanthanum hexaboride The preparation of lanthanum hexaboride and its introduction in or on polymer substrates is well known in the art (see, eg, US Pat. Nos. 6,620,872 and 6,911,254). Lanthanum hexaboride is available, for example, as a dispersion of solid particles in a liquid, optionally containing zirconium and a dispersant.

  Lanthanum hexaboride can be introduced into the polymer sheet of the present invention in any suitable amount, and is generally sufficient to provide the desired near infrared absorption, with undue influence on optical performance. Introduced in an amount that does not give In various embodiments, the lanthanum hexaboride is incorporated into the polymer sheet in an amount of 0.005 to 0.1 wt%, 0.01 to 0.05 wt%, or 0.01 to 0.04 wt%. be introduced. In embodiments where other infrared absorbers are used, the amount of lanthanum hexaboride can be reduced appropriately. Examples of other useful infrared absorbers include indium tin oxide and doped tin oxide.

  Lanthanum hexaboride into polymer sheets, especially poly (vinyl butyral) sheets, for example, lanthanum hexaboride into a melt containing poly (vinyl butyral), a plasticizer, and optionally other additives. It can be introduced by melt mixing. Lanthanum hexaboride can also be introduced onto the already formed polymer sheet using, for example, spraying or dipping methods.

  Lanthanum hexaboride useful in the present invention is nano-sized ground particles and can be, for example, less than 250 nanometers, less than 200 nanometers, less than 150 nanometers, or less than 100 nanometers in size.

Epoxy Agents Any suitable epoxy agent can be used in the present invention as is known in the art (see, eg, US Pat. Nos. 5,529,848 and 5,529,849).

  In various embodiments, as described below, an epoxy composition that has been found to be usable is (a) an epoxy resin primarily comprising the diglycidyl ether of the monomer bisphenol-A; (b) An epoxy resin mainly comprising the diglycidyl ether of monomeric bisphenol-F; (c) an epoxy resin mainly comprising the diglycidyl ether of hydrogenated bisphenol-A; (d) a polyepoxidized phenol novolak; (e) a diepoxide of polyglycol, or Also known as epoxy-terminated polyethers; and (f) selected from a mixture of any of the preceding (a) to (e) epoxy resins (Encyclopedia of Polymer Science and Technology, Volume 6, 1967, Interscience Publishers, NY, pages 209-271).

  A suitable commercially available diglycidyl ether of bisphenol-A of class (a) is DER331 from Dow Chemical Company. The diglycidyl ether of class (b) bisphenol-F epoxy is EPON resin DPL-862 and the diglycidyl ether of class (c) hydrogenated bisphenol-A epoxy is EPONEX resin 1510, both from Shell Chemical Company. Available. Class (d) polyepoxidized phenol formaldehyde novolak is available from Dow Chemical as DEN431. A diepoxide of class (e) poly (oxypropylene) glycol is available as DER732 from Dow Chemical.

  Further examples of suitable epoxy agents include 3,4-epoxycyclohexanecarboxylate compositions of the type described in US Pat. No. 3,723,320. Also useful are diepoxides, such as those described in US Pat. No. 4,060,067, which include two bonded cyclohexane groups each having an epoxide group bonded thereto. Such diepoxide compounds have the formula:

（式中、Ｒ_３は、１から１０個の炭素原子、０から６個の酸素原子、および０から６個の窒素原子を含む有機基であり、Ｒ_４からＲ_９は、独立に、水素および１から５個の炭素原子を含む脂肪族基の中から選択される）に相当する。ジエポキシドの例としては、３，４−エポキシシクロヘキシルメチル−３，４−エポキシシクロヘキサン、ビス（３，４−エポキシ−６−メチルシクロヘキシルメチルアジペート）、および２−（３，４−エポキシシクロヘキシル）−５，５−スピロ（３，４−エポキシ）シクロヘキサン−ｍ−ジオキサンが挙げられる。

Wherein R ₃ is an organic group containing 1 to 10 carbon atoms, 0 to 6 oxygen atoms, and 0 to 6 nitrogen atoms, and R ₄ to R ₉ are independently hydrogen And an aliphatic group containing 1 to 5 carbon atoms). Examples of diepoxides include 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane, bis (3,4-epoxy-6-methylcyclohexylmethyl adipate), and 2- (3,4-epoxycyclohexyl) -5. , 5-spiro (3,4-epoxy) cyclohexane-m-dioxane.

  A further useful epoxy is 2-ethylhexyl glycidyl ether (available as Resolution Modifier 116 from Resolution Products, Houston, Texas).

  Further useful epoxies include diepoxides of poly (oxypropylene) glycol, 2-ethylhexyl glycidyl ether, and diepoxide products of epichlorohydrin and polypropylene glycol.

  Mixtures of epoxy agents can also be used.

  The epoxy agent can be introduced in any suitable amount, taking into account the type of epoxy agent, the composition of the polymer sheet and the determination of the amount of lanthanum hexaboride.

  In various embodiments, the epoxy agent is in a weight ratio of 0.1 to 10.0, 0.1 to 5.0, 0.5 to 4.0, or 1.0 to 3.5 of the polymer sheet. be introduced. These values can be combined in any combination with the values given above for lanthanum hexaboride.

Polymer Film As used herein, “polymer film” means a relatively thin hard polymer layer that functions as a performance enhancing layer. A polymer film is used herein in that the polymer film itself does not provide the necessary penetration resistance and glass retention for a multi-layered glazing structure, but rather provides performance improvements, such as infrared absorption properties, etc. Different from the polymer sheet to be made. Poly (ethylene terephthalate) is most commonly used as a polymer film.

  In various embodiments, the polymer film layer has a thickness of 0.013 mm to 0.20 mm, preferably 0.025 mm to 0.1 mm, or 0.04 to 0.06 mm. The polymeric film layer can optionally be surface treated or coated to improve one or more properties, such as adhesion or infrared radiation reflection. Examples of these functional layers include a multilayer stack for reflecting infrared solar radiation and transmitting visible light when exposed to sunlight. This multi-layer stack is known in the art (see, eg, WO 88/01230 and US Pat. No. 4,799,745), for example, one or more angstrom-thick metal layers and one or more (eg, Two) sequentially deposited and optionally cooperating dielectric layers. As is also known (see, for example, US Pat. Nos. 4,176,661 and 4,786,783), the metal layer is optionally heated to defrost or defrost any associated glass layer. It may be.

  A further type of polymer film that can be used in the present invention is the many described in US Pat. No. 6,797,396 that function to reflect infrared radiation without creating interference caused by the metal layer. Including non-metallic layers.

  The polymer film layer, in some embodiments, is optically transparent (i.e., an object adjacent to one side of the layer can be easily viewed with the eyes of a particular observer looking through this layer from the other side. And, in some embodiments, have a significantly higher tensile modulus, usually larger than any adjacent polymer sheet, usually regardless of composition. In various embodiments, the polymer film layer comprises a thermoplastic material. Among them, thermoplastic materials having suitable properties are nylon, polyurethane, acrylic, polycarbonate, polyolefin such as polypropylene, cellulose acetate and triacetate, vinyl chloride polymer and copolymer, and the like. In various embodiments, the polymer film layer comprises a material such as a restretched thermoplastic film having remarkable properties, such as polyesters such as poly (ethylene terephthalate) and poly (ethylene terephthalate) glycol ( PETG). In various embodiments, poly (ethylene terephthalate) is used, and in various embodiments, poly (ethylene terephthalate) is biaxially stretched to improve strength and is low when exposed to high temperatures. It has shrinkage properties (for example, less than 2% shrinkage in two directions after 30 minutes at 150 ° C.).

  Various coating and surface treatment methods for poly (ethylene terephthalate) films that can be used in the present invention are disclosed in published European Application No. 0157030. The polymer film of the present invention may also include a handcoat and / or an antifog layer known in the art.

Polymer Sheet The following section describes various materials that can be used to form the polymer sheet of the present invention, such as poly (vinyl butyral).

  As used herein, “polymer sheet” refers to a suitable single or more than one layer for use as an intermediate layer that provides suitable penetration resistance and glass retention to a laminated glass panel. Means any thermoplastic polymer formed by any suitable method into a thin layer in the stack. Plasticized poly (vinyl butyral) is most commonly used to form polymer sheets.

  As used herein, “resin” means a polymer (eg, poly (vinyl butyral)) component that is removed from a mixture resulting from an acid catalyzed reaction and subsequent neutralization of the polymer precursor. Resins generally have other components in addition to the polymer, such as acetates, salts, and alcohols. As used herein, “melt” means a molten mixture of resin with a plasticizer and optionally other additives.

  The polymer sheet of the present invention can comprise any suitable polymer, and in preferred embodiments, as exemplified above, the polymer sheet comprises poly (vinyl butyral). In any of the embodiments of the invention provided herein, wherein the polymer component comprises poly (vinyl butyral) as the polymer component of the polymer sheet, the polymer component comprises poly (vinyl butyral) or other comprised of poly (vinyl butyral) Embodiments are included. In these embodiments, any of the types in the plasticizer-containing additive disclosed herein includes a polymer comprising or consisting essentially of poly (vinyl butyral). Can be used with sheets.

  In one embodiment, the polymer sheet comprises a polymer based on partially acetalized poly (vinyl alcohol). In other embodiments, the polymer sheet comprises a polymer selected from the group consisting of poly (vinyl butyral), polyurethane, poly (vinyl chloride), poly (ethylene vinyl acetate), combinations thereof, and the like. In further embodiments, the polymer sheet comprises poly (vinyl butyral) and one or more other polymers. Other polymers with appropriate glass transition temperatures can also be used. Preferred ranges, values, and / or methods, particularly for poly (vinyl butyral) (for example, but not limited to plasticizers, component proportions, thicknesses, and property-enhancing additives) In any of the portions of the specification given here, these ranges also apply to other polymers and polymer blends disclosed herein as useful ingredients in polymer sheets, if applicable. Also apply.

Poly (vinyl butyral) for embodiments containing poly (vinyl butyral) can be made by known acetalization methods known to those skilled in the art (see, eg, US Pat. Nos. 2,282,057 and 2,282,026). I want to be) In one embodiment, B.I. E. According to Wade, Encyclopedia of Polymer Science & Technology , 3 rd edition, solvent method in which are described in Vinyl Acetal Polymers in Volume 8,381 pp. -399 (2003) can be used. In other embodiments, the aqueous methods described therein can be used. Poly (vinyl butyral) can be obtained, for example, from Solutia Inc. , St. Commercially available as Butvar ™ resin from Louis, Missouri.

  In various embodiments, the polymer sheet resin comprising poly (vinyl butyral) is from 10 to 35 wt% (wt%) hydroxyl groups calculated as poly (vinyl alcohol), 13 calculated as poly (vinyl alcohol). Contains 30% by weight hydroxyl groups, or 15 to 22% by weight (wt%) hydroxyl groups calculated as poly (vinyl alcohol). The polymer sheet resin may also contain less than 15 wt% residual ester groups, 13 wt%, 11 wt%, 9 wt%, 7 wt%, 5 wt%, or 3 wt% residual ester groups calculated as polyvinyl acetate. The remainder is acetal, preferably butyraldehyde acetal, but optionally contains other acetal groups, such as 2-ethylhexanal groups (see, for example, US Pat. No. 5,137,954). ).

  In various embodiments, the polymer sheet is at least 30,000, 40,000, 50,000, 55,000, 60,000, 65,000, 70,000, per mole (g / mole or dalton). Poly (vinyl butyral) having a molecular weight of 120,000, 250,000, or at least 350,000 g. Small amounts of dialdehyde or trialdehyde can also be added during the acetalization process to increase molecular weight to at least 350,000 g / mole (eg, US Pat. Nos. 4,902,464; 4,874,814; 4,814,529). No .; and 4654179). As used herein, the term “molecular weight” means weight average molecular weight.

  Various adhesion control agents can be used in the polymer sheets of the present invention, including sodium acetate, potassium acetate, and magnesium salts. Magnesium salts that can be used in these embodiments of the invention are those described in US Pat. No. 5,728,472, for example, magnesium salicylate, magnesium nicotinate, magnesium di- (2-aminobenzoate), Examples include, but are not limited to, magnesium di- (3-hydroxy-2-naphthoate) and magnesium bis (2-ethylbutyrate) (Chemical Abstract No. 79992-76-0). In various embodiments of the present invention, the magnesium salt is magnesium bis (2-ethylbutyrate). Since epoxy agents tend to increase the adhesion of polymer sheets, relatively large amounts of adhesion modifiers are commonly used in the interlayers of the present invention.

  Other additives may be introduced into the polymer sheet to enhance performance in the final product. Such additives include dyes, pigments, stabilizers (eg, UV stabilizers), antioxidants, anti-tacking agents, additional IR absorbers, flame retardants, and other additives known in the art. However, it is not limited to these.

  In various embodiments of the present invention, the polymer sheet can comprise 20 to 60, 25 to 60, 20 to 80, 10 to 70, or 10 to 100 parts plasticizer phr. Of course, other amounts can be used as appropriate for a particular application. In some embodiments, the plasticizer has a hydrocarbon moiety of less than 20, less than 15, less than 12, or less than 10 carbon atoms.

The amount of plasticizer can be adjusted to affect the glass transition temperature (T _g ) of the poly (vinyl butyral) sheet. Generally, higher amounts of plasticizer are added to reduce _Tg . Poly (vinyl butyral) polymer sheets of the present invention, 40 ° C. or less, 35 ° C. or less, 30 ° C. or less, 25 ° C. or less, it is possible to have a 20 ° C. or less, and 15 ℃ below _{T g.}

Any suitable plasticizer can be added to the polymer resin of the present invention to form a polymer sheet. Examples of the plasticizer used in the polymer sheet of the present invention include polybasic acids or esters of polyhydric alcohols. Suitable plasticizers include, for example, triethylene glycol di- (2-ethylbutyrate), triethylene glycol di- (2-ethylhexanoate), triethylene glycol diheptanoate, tetraethylene glycol diheptano , Dihexyl adipate, dioctyl adipate, hexyl cyclohexyl adipate, a mixture of heptyl and nonyl adipate, diisononyl adipate, heptyl nonyl adipate, dibutyl sebacate, oil modified sebacic acid alkyd, etc., disclosed in US Pat. No. 3,841,890 And a mixture of phosphates and adipates, adipates as disclosed in US Pat. No. 4,144,217, and mixtures and combinations of the foregoing. Other plasticizers that can be used are C ₄ to C ₉ alkyl alcohols and cyclo C ₄ to C ₁₀ alcohols disclosed in US Pat. No. 5,013,797, and C ₆ to C ₈ adipate esters such as hexyl adipate. It is a mixed adipate made. In various embodiments, the plasticizer used is dihexyl adipate and / or triethylene glycol di-2-ethylhexanoate.

  The poly (vinyl butyral) polymer, plasticizer, and optional additives can be thermally processed and made into sheet form by methods known to those skilled in the art. One exemplary method of forming a poly (vinyl butyral) sheet is to apply a force to the melt through a die (eg, a die having an opening in which one dimension is substantially larger than the vertical dimension) to form a resin, Extruding molten poly (vinyl butyral) containing a plasticizer and an additive. Another exemplary method of forming a poly (vinyl butyral) sheet includes casting a melt from a die onto a rotor, solidifying the resin, and then removing the solidified resin as a sheet. In various embodiments, the polymer sheet is, for example, from 0.1 to 2.5 millimeters, 0.2 to 2.0 millimeters, 0.25 to 1.75 millimeters, and 0.3 to 1.5 millimeters. Can have a thickness.

  For each of the embodiments described above that include a glass layer, there are other embodiments where non-glass sheet glass type materials are used in place of glass, where appropriate. Examples of such glazing layers are hard plastics with high glass transition temperatures, for example glass transition temperatures above 60 ° C. or 70 ° C., such as polycarbonate and polyalkyl methacrylates, in particular 1 to 3 in the alkyl part. And polyalkyl methacrylates having the following carbon atoms.

  The present invention also includes any polymer sheet and intermediate layer stack or roll disclosed herein in any combination.

  The present invention also includes windshields, windows, and other final glazing products that include any of the interlayers of the present invention.

  The present invention includes a method for producing an intermediate layer and a glass sheet panel comprising the step of forming an intermediate layer or glass sheet panel of the present invention using any of the polymer sheets of the present invention described herein. .

  Also herein, infrared and / or near infrared through the opening, including the step of placing any of the polymer sheet structures of the present invention in the opening, eg, in a windshield or sheet glass panel. Methods for reducing the transmission of radiation are also included within the scope of the present invention.

  The present invention further provides a method for producing a polymer sheet comprising the steps of mixing an epoxy agent and lanthanum hexaboride in a melt of any of the polymers described herein and then forming the polymer sheet. Including.

  Various polymer sheets and / or laminated glass properties and methods of measurement are described for use in the present invention.

  The transparency of the polymer sheet can be determined by measuring the haze value, which is a quantification of the scattered light of the sample relative to the incident light. The haze rate can be measured by the following apparatus. A device for measuring the amount of haze, a transmissometer, Model D25, is available from Hunter Associates (Reston, Va.) And uses ASTM D1003-61 (using light source C at an observer angle of 2 °. (Revised 1977)-can be used in accordance with Procedure A. In various embodiments of the invention, the haze rate is less than 5%, less than 3%, and less than 1%.

  Pummel adhesion can be measured by the following method, where “shock” as used herein means quantifying the adhesion of the polymer sheet to the glass. The following method is used to determine the attack. Two-ply glass laminate samples are prepared under standard autoclave lamination conditions. The laminate is cooled to about −17 ° C. (0 ° F.) and struck manually with a hammer until the glass breaks. Then, all broken glass not adhered to the poly (vinyl butyral) sheet is removed and the amount of glass remaining adhered to the poly (vinyl butyral) sheet is visually compared with the set criteria. This standard corresponds to a scale in which the degree of glass remaining adhered to the poly (vinyl butyral) sheet varies. In particular, at zero impact criteria, the glass does not remain adhered to the poly (vinyl butyral) sheet. With an impact criteria of 10, 100% of the glass remains adhered to the poly (vinyl butyral) sheet. In the laminated glass panel of the present invention, various embodiments have at least 3, at least 5, at least 8, at least 9, or 10 strikes. Other embodiments have an impact between 8 and 10.

  The “yellowness” of the polymer sheet can be measured by: forming a transparent molded disk of polymer sheet, 1 cm thick, having an essentially planar, parallel and smooth polymer surface. The yellowness is measured from the spectral light transmission in the visible spectrum by ASTM method D1925, “Standard Test Method for Yellowness Index of Plastics”. Values are corrected for 1 cm thickness using the measured sample thickness.

  As used herein, “average particle size” is calculated by direct measurement of electron microscopic images of a number of dispersed particles.

Example 1
Six polymer sheets are formed having the composition shown in the table below (all numbers are given as weight percent). Lanthanum hexaboride based on the KHV-11 dispersion contains relatively low concentrations of relatively large particles (approximately 200 nanometers) that cause visible light scattering. To reduce visible light scattering, a reduced particle size lanthanum hexaboride particle dispersion KHDV-05A is used. However, these small particles are more susceptible to hydrolysis than the large particles in KHV-11. The additive is premixed with poly (vinyl butyral) and blended during sheet extrusion in a single screw extruder. A 0.76 mm thick sheet is extruded using a sheet die.

６枚のポリマーシートを、２枚の２．３ミリメートル厚のガラスシートの間に積層する。６枚の得られた複数層積層板ガラスパネルについて、パネルの縁部において、１，０００ナノメートルの光線の透過率を測定する。結果を記録し、次いで、６枚のパネルを、５０℃、９５％相対湿度の環境に置く。パネルの縁部において、１，０００ナノメートルの光線の透過率の更なるサンプリングを９週間行う。結果は図１において示される。

Six polymer sheets are laminated between two 2.3 millimeter thick glass sheets. The transmittance of a light beam of 1,000 nanometers is measured at the edge of the six laminated multilayer glass sheet panels obtained. The results are recorded and then the six panels are placed in an environment of 50 ° C. and 95% relative humidity. At the edge of the panel, a further sampling of the light transmission of 1,000 nanometers is performed for 9 weeks. The result is shown in FIG.

  Six multi-layer glazing laminates are also sampled over 9 weeks for transmission at 1,000 nanometers in the center of the panel. The ratio of transmittance at 1,000 nanometers at the edge of each panel to the center of these same panels over 4 weeks is shown in FIG.

  FIG. 3 is a graph showing transmission spectra at initial, 4 and 9 weeks for a multi-layer glazing panel formed from polymer sheets with reference numbers 1 and 3.

  In accordance with the present invention, intermediate layers having excellent selective infrared transmission reduction properties, such as poly (vinyl butyral) sheets, and other polymers that are resistant to degradation caused by environmental factors. Sheets and the like can be provided.

  Although the present invention has been described with reference to exemplary embodiments, various modifications can be made and equivalents can be substituted for these elements without departing from the scope of the invention. It will be understood by those skilled in the art. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the invention without departing from the essential scope thereof. Accordingly, the invention is not limited to the specific embodiments disclosed as the best mode contemplated for carrying out the invention, but the invention includes all implementations that fall within the scope of the appended claims. It is intended to include forms.

  Further, any ranges, values, or characteristics given for any single component of the present invention, where compatible, values defined for each of the components given throughout this specification. It is understood that any range, value, or characteristic given for any other component of the invention can be used interchangeably to form an embodiment having For example, if desired, in addition to including an epoxy agent in any given range, in order to form a number of substitutions that are within the scope of the present invention but cumbersome to enumerate A range of polymer sheets containing lanthanum hexaboride can be formed.

  The reference numbers in any figures provided within the abstract or claims are for illustrative purposes only and are referenced to any one particular embodiment shown in any figure. It should not be construed as limited to the invention.

  The scale is not drawn unless otherwise indicated.

  Each reference, including academic journal articles, patents, applications, and books, referred to herein is hereby incorporated by reference in its entirety.

FIG. 5 shows a graph showing the light transmission of 1,000 nanometers for six glass laminates over time at 50 ° C. and 95% relative humidity. FIG. 7 shows a graph showing the edge / internal ratio of light transmission of 1,000 nanometers over a period of 6 glass laminates at 50 ° C. and 95% relative humidity. FIG. 4 shows a graph showing the spectral curves of two glass laminates at two time points set at the edge of the glass laminate at 50 ° C. and 95% relative humidity.

Claims (18)

Lanthanum hexaboride, and
A multi-layer flat glass interlayer comprising an epoxy agent selected from the group consisting of aliphatic monoepoxides and aliphatic diepoxides .   The interlayer of claim 1, wherein the epoxy agent is selected from the group consisting of polyepoxyglycol diepoxide, 2-ethylhexyl glycidyl ether, and epichlorohydrin and polypropylene glycol diepoxide products.   The intermediate layer of claim 1, wherein the epoxy agent is present in an amount of 0.1 to 10.0 wt%.   The intermediate layer of claim 1, wherein the epoxy agent is present in an amount of 0.5 to 4.0 wt%.   The interlayer of claim 1, wherein the lanthanum hexaboride is present in an amount of 0.005 to 0.1 wt%.   The intermediate layer of claim 1, wherein the lanthanum hexaboride is present in an amount of 0.005 to 0.05 wt%.   The interlayer of claim 1 wherein the epoxy agent is present in an amount of 0.1 to 10.0 wt% and the lanthanum hexaboride is present in an amount of 0.005 to 0.1 wt%.   The interlayer of claim 1 wherein the epoxy agent is present in an amount of 0.5 to 4.0 wt% and the lanthanum hexaboride is present in an amount of 0.005 to 0.05 wt%.   The intermediate layer of claim 1, wherein the intermediate layer comprises poly (vinyl butyral). The interlayer of claim 9 , wherein the epoxy agent is selected from the group consisting of diepoxide of poly (oxypropylene) glycol, 2-ethylhexyl glycidyl ether, and diepoxide product of epichlorohydrin and polypropylene glycol. The interlayer of claim 9 , wherein the epoxy agent is present in an amount of 0.1 to 10.0 wt%. The interlayer of claim 9 , wherein the epoxy agent is present in an amount of 0.5 to 4.0 wt%. The intermediate layer of claim 9 , wherein the lanthanum hexaboride is present in an amount of 0.005 to 0.1 wt%. The interlayer of claim 9 , wherein the lanthanum hexaboride is present in an amount of 0.005 to 0.05 wt%. The interlayer of claim 9 , wherein the epoxy agent is present in an amount of 0.1 to 10.0 wt%, and the lanthanum hexaboride is present in an amount of 0.005 to 0.1 wt%. The interlayer of claim 9 , wherein the epoxy agent is present in an amount of 0.5 to 4.0 wt% and the lanthanum hexaboride is present in an amount of 0.005 to 0.05 wt%. Lanthanum hexaboride, and
A multi-layer plate glass comprising an intermediate layer comprising an epoxy agent selected from the group consisting of aliphatic monoepoxides and aliphatic diepoxides . Forming a melt comprising lanthanum hexaboride and epoxy agents, and the intermediate layer observed including that formed from the melt,
The epoxy agent is selected from the group consisting of aliphatic monoepoxides and aliphatic diepoxides
A method for producing a multi-layer glass sheet intermediate layer.

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